Biradical states of oxygen-vacancy defects in ��-quartz: centers E_{2}^{\prime \prime } and E_{4}^{\prime \prime }

Several new radiation defects with total electron spin S?=?1 occurring in electron-irradiated, synthetic ??-quartz have been observed by using electron paramagnetic resonance spectroscopy. These defects are considered to be biradicals, i.e., pairs of S?=?1/2 species. The concentration of these centers depends on the condition of the fast-electron irradiation. They have different decay behaviors that allow measurements of any individual species especially when it predominates over the others. The primary spin Hamiltonian parameter matrices g ₁, g ₂, D have now been determined for two similar defects, which herein are labeled $ E_{2}^{\prime \prime } $ and $ E_{4}^{\prime \prime } $ . Inter-electron distances estimated by using the magnetic dipole model, suggest that the structures of centers $ E_{2}^{\prime \prime } $ and $ E_{4}^{\prime \prime } $ both involve the unpaired electrons each located in orbitals of two silicon atoms next to a common oxygen vacancy but which have slightly different Si?CSi distances at 0.90 and 0.79?nm, respectively. This model is consistent with previous DFT calculations of the triplet configurations with local energetic minima. Observed decay behaviors suggest a transformation of centers $ E_{2,4}^{\prime \prime } $ to the analogous $ E_{1}^{\prime \prime } $ center. These triplet centers in quartz provide new insights into the structures of analogous defects in amorphous silica.     

The calcium oxotellurate(IV) nitrates Ca5Te4O12(NO3)2(H2O)2 and Ca6Te5O15(NO3)2

Single crystals of two novel calcium oxotellurate(IV) nitrates were grown under hydrothermal conditions and were structurally characterized by X-ray diffraction. Ca $_5$ Te $_4\text {O}_{12}$ (NO $_3$ ) $_2$ (H $_2$ O) $_2$ [ $Cc$ , $Z=4$ , $a=25.258(3)$ Å, $b=5.7289(7)$ Å, $c=17.0066(19)$ Å, $\beta =124.377(2)^{\circ}$ , $R[F^2 > 2\sigma (F^2)]=0.043$ , 4083 $F^2$ data, 281 parameters] can be described as a non-classic order/disorder (OD) structure, which fulfills the basic principle of OD theory, viz. local equivalence of polytypes, but does not strictly follow the vicinity condition (VC) of OD theory. The structure is made up from an alternating stacking of non-polar layers composed of isolated [TeO $_3$ ] units and Ca $^{2+}$ ions and polar layers containing NO $_3^-$ ions and water molecules. The electron lone-pairs of the [TeO $_3$ ] units protrude into the free space of the anion/water layers. The crystal under investigation was a non-classic OD-twin of domains of a maximum degree of order (MDO). At the twin plane a fragment of the second MDO polytype is located. The main building blocks of Ca $_6$ Te $_5\text {O}_{15}$ (NO $_3$ ) $_2$ [ $P2_1/c$ , $Z=4$ , $a=15.494(2)$ Å, $b=5.6145(7)$ Å, $c=39.338(4)$ Å, $\beta =142.480(5)^{\circ}$ , $R[F^2 > 2\sigma (F^2)]=0.043$ , 3026 $F^2$ data, 307 parameters] are isolated [TeO $_3$ ] units and Ca $^{2+}$ ions which are connected to a three-dimensional framework perforated by channels in which the N atoms of the nitrate anions are located and the electron lone-pairs of the [TeO $_3$ ] units protrude. The structure can topologically be derived from the structure of Ca $_5$ Te $_4\text {O}_{12}$ (NO $_3$ ) $_2$ (H $_2$ O) $_2$ by removing the water molecules and connecting the CaTeO $_3$ layers with additional [TeO $_3$ ] units and Ca $^{2+}$ ions.     

The dilatant behaviour of sand–pile interface subjected to loading and stress relief

Property and behaviour of sand–pile interface are crucial to shaft resistance of piles. Dilation or contraction of the interface soil induces change in normal stress, which in turn influences the shear stress mobilised at the interface. Although previous studies have demonstrated this mechanism by laboratory tests and numerical simulations, the interface responses are not analysed systematically in terms of soil state (i.e. density and stress level). The objective of this study is to understand and quantify any increase in normal stress of different pile–soil interfaces when they are subjected to loading and stress relief. Distinct element modelling was carried out. Input parameters and modelling procedure were verified by experimental data from laboratory element tests. Parametric simulations of shearbox tests were conducted under the constant normal stiffness, constant normal load and constant volume boundary conditions. Key parameters including initial normal stress ( $ \sigma_{{{\text{n}}0}}^{\prime } $ ), initial void ratio (e ₀), normal stiffness constraining the interface and loading–unloading stress history were investigated. It is shown that mobilised stress ratio ( $ \tau /\sigma_{\text{n}}^{\prime } $ ) and normal stress increment ( $ \Updelta \sigma_{\text{n}}^{\prime } $ ) on a given interface are governed by $ \sigma_{{{\text{n}}0}}^{\prime } $ and e ₀. An increase in $ \sigma_{{{\text{n}}0}}^{\prime } $ from 100 to 400 kPa leads to a 30 % reduction in $ \Updelta \sigma_{\text{n}}^{\prime } $ . An increase in e ₀ from 0.18 to 0.30 reduces $ \Updelta \sigma_{\text{n}}^{\prime } $ by more than 90 %, and therefore, shaft resistance is much lower for piles in loose sands. A unique relationship between $ \Updelta \sigma_{\text{n}}^{\prime } $ and normal stiffness is established for different soil states. It can be applied to assess the shaft resistance of piles in soils with different densities and subjected to loading and stress relief. Fairly good agreement is obtained between the calculated shaft resistance based on the proposed relationship and the measured results in centrifuge model tests.     

Analysis of the Influence of a Natural Fracture Network on Hydraulic Fracture Propagation in Carbonate Formations

A new experimental model has been designed to simulate the influence of a natural fracture network on the propagation geometry of hydraulic fractures in naturally fractured formations using a tri-axial fracturing system. In this model, a parallel and symmetrical pre-fracture network was created by placing cement plates in a cubic mold and filling the mold with additional cement to create the final testing block. The surface of the plates will thus be weakly cemented and form pre-fractures. The dimension and direction of the pre-fractures can be controlled using the plates. The experiments showed that the horizontal differential stress $\Updelta \sigma$ and the angle $\Updelta \theta$ between the maximum horizontal principal in situ stress and the pre-fracture are the dominating factors for the initiation and propagation of hydraulic fractures. For $\Updelta \theta = 90^\circ$ and $\Updelta \sigma \ge 2{\text{ MPa}}$ or $\Updelta \theta = 60^\circ$ and $\Updelta \sigma \ge 4{\text{ MPa}}$ , the direction of the initiation and propagation of the hydraulic fractures are consistent with or deviate from the normal direction of the pre-fracture. When the hydraulic fractures approach the pre-fractures, the direction of the hydraulic fracture propagation will be consistent with the normal direction of the pre-fracture. Otherwise, the hydraulic fracture will deflect and perpendicularly cross the parallel and symmetric pre-fracture network. For $\Updelta \theta = 90^\circ$ and $\Updelta \sigma < 2{\text{ MPa}},\,\Updelta \theta = 60^\circ$ , and $\Updelta \sigma < 4{\text{ MPa}}$ or $\Updelta \theta = 45^\circ$ and $\Updelta \sigma = 4 - 8{\text{ MPa}}$ , before the hydraulic fracture and the pre-fractures intersect, the direction of the hydraulic fracture propagation remains unchanged, and the pre-fractures open or dilate when the hydraulic fracture propagates to the intersection point, forming a complicated hydraulic fracture network with the propagation region of the overall hydraulic fracture network taking the shape of an ellipse. In this condition, the complexity level of the hydraulic fracture is controlled by the net pressure, the compressive normal stress acting on the pre-fractures, the shearing strength and the cohesion strength of the planes of weakness. The conclusions of this research are inconsistent with the formulation of the approach angle that has been widely accepted by previous studies. The principle of hydraulic fracture propagation is that it follows the least resistance, the most preferential propagation, and the shortest propagation path.     

Crystallographic preferred orientation in wüstite (FeO) through the cubic-to-rhombohedral phase transition

Magnesiowüstite, (Mg_0.08Fe_0.88)O, and wüstite, Fe_0.94O, were compressed to ~36?GPa at ambient temperature in the diamond anvil cell (DAC) at the Advanced Light Source. X-ray diffraction patterns were taken in situ in radial geometry in order to study the evolution of crystallographic preferred orientation through the cubic-to-rhombohedral phase transition. Under uniaxial stress in the DAC, {100}_c planes aligned perpendicular to the compression direction. The {100}_c in cubic became { $\left\{ {10\bar 14} \right\}$ }_r in rhombohedral and remained aligned perpendicular to the compression direction. However, the {101}_c and {111}_c planes in the cubic phase split into { ${10{\bar{1}}4}$ }_r and { ${11{\bar{2}}0}$ }_r, and (0001)_r and { ${10{\bar{1}}1}$ }_r, respectively, in the rhombohedral phase. The { ${11{\bar{2}}0}$ }_r planes preferentially aligned perpendicular to the compression direction while { ${10{\bar{1}}4}$ }_r oriented at a low angle to the compression direction. Similarly, { ${10{\bar{1}}1}$ }_r showed a slight preference to align more closely perpendicular to the compression direction than (0001)_r. This variant selection may occur because the 〈 ${10{\bar{1}}4}$ 〉_r and [0001]_r directions are the softer of the two sets of directions. The rhombohedral texture distortion may also be due to subsequent deformation. Indeed, polycrystal plasticity simulations indicate that for preferred { ${10{\bar{1}}4}$ }〈 ${1{\bar{2}}10}$ 〉_r and { ${11{\bar{2}}0}$ }〈 ${{\bar{1}}101}$ 〉_r slip and slightly less active { ${10{\bar{1}}1}$ }〈 ${{\bar{1}}2{\bar{1}}0}$ 〉_r slip, the observed texture pattern can be obtained.     

Experimental Investigation of Seepage Properties of Fractured Rocks Under Different Confining Pressures

The effectiveness of transmitting underground water in rock fractures is strongly influenced by the widths of the fractures and their interconnections. However, the geometries needed for water flow in fractured rock are also heavily controlled by the confining pressure conditions. This paper is intended to study the seepage properties of fractured rocks under different confining pressures. In order to do this, we designed and manufactured a water flow apparatus that can be connected to the electro-hydraulic servo-controlled test system MTS815.02, which provides loading and exhibits external pressures in the test. Using this apparatus, we tested fractured mudstone, limestone and sandstone specimens and obtained the relationship between seepage properties and variations in confining pressure. The calculation of the seepage properties based on the collection of water flow and confining pressure differences is specifically influenced by non-Darcy flow. The results show that: (1) The seepage properties of fractured rocks are related to confining pressure, i.e. with the increase of confining pressure, the permeability $ k $ decreases and the absolute value of non-Darcy flow coefficient $ \beta $ increases. (2) The sandstone coefficients $ k $ and $ \beta $ range from $ 1.03 \times 10^{ - 18} $ to $ 1.53 \times 10^{ - 17} $  m² and $ - 1.13 \times 10^{17} $ to $ - 2.35 \times 10^{18} $  m^?1, respectively, and exhibit a greater change compared to coefficients of mudstone and limestone. (3) From the regression analysis of experimental data, it is concluded that the polynomial function is a better fit than the power and logarithmic functions. The results obtained can provide an important reference for understanding the stability of rock surrounding roadways toward prevention of underground water gushing-out, and for developing underground resources (e.g. coal).     

The thermodynamics of the I \overline{1} –P \overline{1} phase transition in Ca-rich plagioclase from an assessment of the spontaneous strain

In-situ powder diffraction measurements between 90 and 935?K on four anorthite-rich plagioclase samples (An₁₀₀, An₉₆Ab₄, An₈₉Ab₁₁ and An₇₈Ab₂₂) were used to determine the detailed evolution of these samples through the $I \overline{1} $ – $P \overline{1} $ phase transition. The c-type reflections indicative of $P \overline{1} $ symmetry were detected only in An₁₀₀, An₉₆Ab₄, whereas deviations in the evolution of the unit-cell parameters with temperature were observed in all samples, most prominently in the β unit-cell angle. The c-type reflections disappear at ~510 and ~425?K in An₁₀₀ and An₉₆Ab₄ respectively, and their intensity decreases according to a tricritical trend $ I^{2} \propto \left( {T - T_{\text{c}} } \right) $ . The cell parameter changes were used to determine the spontaneous strains arising from the transition which were modelled with Landau theory, allowing for low-temperature quantum saturation, in order to determine the thermodynamic behaviour. In An₁₀₀ tricritical behaviour was observed [T _c?=?512.7(4)?K; θ_s?=?394(4)] in good agreement with previous studies, and the c-type superlattice reflections indicative of $P \overline{1} $ symmetry persist up to the T _c determined from the spontaneous strain, and then disappear. The evolution of the spontaneous strain in An₉₆Ab₄ is tricritical at low temperatures [T _c?=?459(1) K, θ_s?=?396(5)] up to the temperature of disappearance of c-type reflections, but becomes second order beyond ~440?K. In An₈₉Ab₁₁ the strain displays second-order behaviour throughout [T _c?=?500(1) and θ_s?=?212(5)], and the c-type reflections are not detected in the powder diffraction patterns at any temperature. The apparent discrepancy between the absence of c-type reflections in temperature ranges where the cell parameters display significant spontaneous strain is resolved through consideration of the sizes of the anti-phase domains within the crystals. It is deduced that the tricritical phase transition occurs in well-ordered crystals with large domains in which the behavior of individual domains is dominant (i.e. in pure anorthite) or where the $P \overline{1} $ distortions within the domains are large enough to dominate the structural coherency strains between the domains. When both the magnitude of the $P \overline{1} $ pattern of displacements of the tetrahedral framework become smaller and the influence of the structural coherency between anti-phase domains becomes significant, the thermodynamic behavior becomes 2nd-order in character, the c-type reflections disappear, and the orientation of the spontaneous strain changes.     

An experimental study of Ti and Zr partitioning among zircon, rutile, and granitic melt

In order to evaluate the effect of trace and minor elements (e.g., P, Y, and the REEs) on the high-temperature solubility of Ti in zircon (zrc), we conducted 31 experiments on a series of synthetic and natural granitic compositions [enriched in TiO₂ and ZrO₂; Al/(Na + K) molar ~1.2] at a pressure of 10 kbar and temperatures of ~1,400 to 1,200 °C. Thirty of the experiments produced zircon-saturated glasses, of which 22 are also saturated in rutile (rt). In seven experiments, quenched glasses coexist with quartz (qtz). SiO₂ contents of the quenched liquids range from 68.5 to 82.3 wt% (volatile free), and water concentrations are 0.4–7.0 wt%. TiO₂ contents of the rutile-saturated quenched melts are positively correlated with run temperature. Glass ZrO₂ concentrations (0.2–1.2 wt%; volatile free) also show a broad positive correlation with run temperature and, at a given T, are strongly correlated with the parameter (Na + K + 2Ca)/(Si·Al) (all in cation fractions). Mole fraction of ZrO₂ in rutile $ \left( {\mathop X\nolimits_{{{\text{ZrO}}_{ 2} }}^{\text{rt}} } \right) $ in the quartz-saturated runs coupled with other 10-kbar qtz-saturated experimental data from the literature (total temperature range of ~1,400 to 675 °C) yields the following temperature-dependent expression: $ {\text{ln}}\left( {\mathop X\nolimits_{{{\text{ZrO}}_{ 2} }}^{\text{rt}} } \right) + {\text{ln}}\left( {a_{{{\text{SiO}}_{2} }} } \right) = 2.638(149) - 9969(190)/T({\text{K}}) $ , where silica activity $ a_{{{\text{SiO}}_{2} }} $ in either the coexisting silica polymorph or a silica-undersaturated melt is referenced to α-quartz at the P and T of each experiment and the best-fit coefficients and their uncertainties (values in parentheses) reflect uncertainties in T and $ \mathop X\nolimits_{{{\text{ZrO}}_{2} }}^{\text{rt}} $ . NanoSIMS measurements of Ti in zircon overgrowths in the experiments yield values of ~100 to 800 ppm; Ti concentrations in zircon are positively correlated with temperature. Coupled with values for $ a_{{{\text{SiO}}_{2} }} $ and $ a_{{{\text{TiO}}_{2} }} $ for each experiment, zircon Ti concentrations (ppm) can be related to temperature over the range of ~1,400 to 1,200 °C by the expression: $ \ln \left( {\text{Ti ppm}} \right)^{\text{zrc}} + \ln \left( {a_{{{\text{SiO}}_{2} }} } \right) - \ln \left( {a_{{{\text{TiO}}_{2} }} } \right) = 13.84\left( {71} \right) - 12590\left( {1124} \right)/T\left( {\text{K}} \right) $ . After accounting for differences in $ a_{{{\text{SiO}}_{2} }} $ and $ a_{{{\text{TiO}}_{2} }} $ , Ti contents of zircon from experiments run with bulk compositions based on the natural granite overlap with the concentrations measured on zircon from experiments using the synthetic bulk compositions. Coupled with data from the literature, this suggests that at T ≥ 1,100 °C, natural levels of minor and trace elements in “granitic” melts do not appear to influence the solubility of Ti in zircon. Whether this is true at magmatic temperatures of crustal hydrous silica-rich liquids (e.g., 800–700 °C) remains to be demonstrated. Finally, measured $ D_{\text{Ti}}^{{{\text{zrc}}/{\text{melt}}}} $ values (calculated on a weight basis) from the experiments presented here are 0.007–0.01, relatively independent of temperature, and broadly consistent with values determined from natural zircon and silica-rich glass pairs.     

A multi-isotope approach for understanding sources of water,carbon and sulfur in natural springs of the Central Appalachian region

Natural springs have been reliable sources of domestic water and have allowed for the development of recreational facilities and resorts in the Central Appalachians. The structural history of this area is complex and it is unknown whether these natural springs receive significant recharge from modern precipitation or whether they discharge old water recharged over geological times scales. The main objective of this study was to use stable isotopes of water ( $\delta^{18} {\text{O}}_{{{\text{H}}_{2} {\text{O}}}}$ and $\delta^{2} {\text{H}}_{{{\text{H}}_{2} {\text{O}}}}$ ), dissolved inorganic carbon ( $\delta^{13} {\text{C}}_{\text{DIC}}$ ) and dissolved sulfate ( $\delta^{34} {\text{S}}_{{{\text{SO}}_{4} }}$ and $\delta^{18} {\text{O}}_{{{\text{SO}}_{4} }}$ ) to delineate sources of water, carbon and sulfur in several natural springs of the region. Our preliminary isotope data indicate that all springs are being recharged by modern precipitation. The oxygen isotope composition indicates that waters in thermal springs did not encounter the high temperatures required for O isotope exchange between the water and silicate/carbonate minerals, and/or the residence time of water in the aquifers was short due to high flow rates. The carbon isotopic composition of dissolved inorganic carbon and sulfur/oxygen isotopic composition of dissolved sulfate provide evidence of low-temperature water–rock interactions and various biogeochemical transformations these waters have undergone along their flow path.     

P wave attenuation structure beneath the Kanto district and surrounding area, Japan

Spectral ratios of teleseismic P waves for 15 deep (>200 km) earthquakes recorded at 146 High-Sensitivity Seismographic Network stations in the Kanto district and its surrounding area, eastern Japan, were inverted for attenuation parameter $ t_P^{ * } $ . The dataset consisted of good-quality vertical-component seismograms, whose P phases were handpicked. The P wave spectral ratios with high signal-to-noise ratios were calculated up to 1 Hz for all the station pairs, linear regressed, and then inverted for $ t_P^{ * } $ using the technique of least squares . The result showed that the active volcanic areas were clearly characterized by high $ t_P^{ * } $ . In contrast, $ t_P^{ * } $ varied in the nonvolcanic areas. The present result on the $ t_P^{ * } $ distribution was roughly consistent with the shallow part (<30 km) of an attenuation structure, which has been previously obtained based on 3-D tomography by using records of high-frequency (around 5 Hz) P waves from local earthquakes. This suggested that the present method of $ t_P^{ * } $ estimation is valid. The advantage and possible application to other areas were also discussed.     

Fitting matrix-valued variogram models by simultaneous diagonalization (Part I: Theory)

Suppose that ¯(x₁),...,¯Z(x_n). are observations of vector-valued random function ¯(x). In the isotropic situation, the sample variogram γ^*(h) for a given lag h is $$\bar \gamma ^ * (h) = \frac{1}{{2N(h)}}\mathop \sum \limits_{s(h)} (\overline Z (x_1 ) - \overline Z (x_1 )) \overline {(Z} (x_1 ) - \overline Z (x_1 ))^T $$ where s(h) is a set of paired points with distance h and N(h) is the number of pairs in s(h).. For a selection of lags h₁, h₂, .... h_k such that N (h₁) > O. we obtain a ktuple of (semi) positive definite matrices $\bar \gamma ^ * (h_{ 1} ),. . . ., \bar \gamma ^ * (h_{ k} )$ . We want to determine an orthonormal matrix B which simultaneously diagonalizes the $\bar \gamma ^ * (h_{ 1} ),. . . ., \bar \gamma ^ * (h_{ k} )$ or nearly diagonalizes them in the sense that the sum of squares of offdiagonal elements is small compared to the sum of squares of diagonal elements. If such a B exists, we linearly transform $\overline Z (x)$ by $\overline Y (x) = B\overline Z (x)$ . Then, the resulting vector function $\overline Y (x)$ has less spatial correlation among its components than $\overline Z (x)$ does. The components of $\overline Y (x)$ with little contribution to the variogram structure may be dropped, and small crossvariograms fitted by straightlines. Variogram models obtained by this scheme preserve the negative definiteness property of variograms (in the matrix-valued function sense). A simplified analysis and computation in cokriging can be carried out. The principles of this scheme arc presented in this paper.     

Bootstrap determination of the reliability of b-values: an assessment of statistical estimators with synthetic magnitude series

We consider some practical issues of the determination of the b-value of sequences of magnitudes with the bootstrap method for short series of length L and various quantization levels $\Updelta m$ of the magnitude. Preliminary Monte Carlo tests performed with $\Updelta m = 0$ demonstrate the superiority of the maximum likelihood estimator b _MLE, and the inconsistency of the, yet often used, b _LR estimator defined as the least-squares slope of the experimental Gutenberg?CRichter curve. The Monte Carlo tests are also applied to an estimator, b _KS, which minimizes the Kolmogorov?CSmirnov distance between the cumulative distribution of magnitudes and a power-law model. Monte Carlo tests of discrete versions of the b _MLE and b _KS estimators are done for $\Updelta m = \{0.1, 0.2, 0.3 \}$ and used as reference to evaluate the performance of the bootstrap determination of b. We show that all estimators provide b estimates within 10?% error for L????100 and if a large number, n?=?2?×?10⁵, of bootstrapped sample series is used. A resolution test done with $\Updelta m = 0.1$ reveals that a clear distinction between b?=?0.8, 1.0, and 1.2 is obtained if L????200.     

Soil responses near Delhi ridge and adjacent regions in Greater Delhi during incidence of a local earthquake

In this study, soil response was carried out for the Greater Delhi region. A folded Proterozoic formation was identified as Delhi ridge, passes through its central part along SSW–NNE direction, and appears to be a main geomorphic feature for the study area. The Delhi ridge is an exposed quartzite rock of about 10–100 m wide and ~25 km long with gentler dipping both toward east and west. We have considered the exposed part as an outcrop side near the ridge axis and the dipping area as rigid base away from the ridge axis for ground motion study during the occurrence of the 25 November 2007 earthquake with magnitude M _L 4.3 (Richter scale) that occurred at Delhi–Haryana State boundary. The degree of shaking was very strong and reported major cracks in the buildings near the epicenter area. We have studied the soil response parameters at the surface level, considering horizontally stratified soil layers above rigid base. The equivalent linear method was used for soil response analysis at 25 sites in Greater Delhi area. The peak amplification factors vary from 3.2 to 5.9 and peak resonance frequency varies from 1.2 to 5.3 Hz. The correlation among the peak amplification factor (A) and frequency (f) was empirically established as A = 0.36f + 3.60. Increasing peak amplification factor was found at sites with increasingly thicker alluvium deposit with lower frequency contains ground motion and vice versa. Seismic zoning map was also reconstructed for peak amplification factors and predominant periods for the study area for the mitigation purposes of earthquake damage. The average shear wave velocity up to 30 m soil depth is also obtained for site classification. The average velocity to 30 m [ $ \overline{{V_{\text{s}} }} (30) $ ] is a widely used parameter for classifying sites for predicting their potentiality to amplify seismic shaking. A lower value [ $ \overline{{V_{\text{s}} }} (30) $ ] thus yields a more conservative estimate of ground motion, which generally increases as $ \overline{{V_{\text{s}} }} (30) $ decreases. Present estimate of $ \overline{{V_{\text{s}} }} (30) $ varies from 315 to 419 m/s. In this study, we have identified two site classes C and D, as per National Earthquake Hazard Reduction Program. The city planner or engineers can directly use these data for site-specific assessment during retrofitting of the existing structure, demolition of the old buildings and design a new structure to avoid major destruction of the buildings due to future earthquake.     

The P–V–T equation of state of CaPtO3 post-perovskite

Orthorhombic post-perovskite CaPtO₃ is isostructural with post-perovskite MgSiO₃, a deep-Earth phase stable only above 100 GPa. Energy-dispersive X-ray diffraction data (to 9.4 GPa and 1,024 K) for CaPtO₃ have been combined with published isothermal and isobaric measurements to determine its P–V–T equation of state (EoS). A third-order Birch–Murnaghan EoS was used, with the volumetric thermal expansion coefficient (at atmospheric pressure) represented by α(T) = α₀ + α₁(T). The fitted parameters had values: isothermal incompressibility, $ K_{{T_{0} }} $  = 168.4(3) GPa; $ K_{{T_{0} }}^{\prime } $  = 4.48(3) (both at 298 K); $ \partial K_{{T_{0} }} /\partial T $  = ?0.032(3) GPa K^?1; α₀ = 2.32(2) × 10^?5 K^?1; α₁ = 5.7(4) × 10^?9 K^?2. The volumetric isothermal Anderson–Grüneisen parameter, δ _T , is 7.6(7) at 298 K. $ \partial K_{{T_{0} }} /\partial T $ for CaPtO₃ is similar to that recently reported for CaIrO₃, differing significantly from values found at high pressure for MgSiO₃ post-perovskite (?0.0085(11) to ?0.024 GPa K^?1). We also report axial P–V–T EoS of similar form, the first for any post-perovskite. Fitted to the cubes of the axes, these gave $ \partial K_{{aT_{0} }} /\partial T $  = ?0.038(4) GPa K^?1; $ \partial K_{{bT_{0} }} /\partial T $  = ?0.021(2) GPa K^?1; $ \partial K_{{cT_{0} }} /\partial T $  = ?0.026(5) GPa K^?1, with δ _T  = 8.9(9), 7.4(7) and 4.6(9) for a, b and c, respectively. Although $ K_{{T_{0} }} $ is lowest for the b-axis, its incompressibility is the least temperature dependent.     

Redox-controlled iron isotope fractionation during magmatic differentiation: an example from the Red Hill intrusion, S. Tasmania

This study presents accurate and precise iron isotopic data for 16 co-magmatic rocks and 6 pyroxene–magnetite pairs from the classic, tholeiitic Red Hill sill in southern Tasmania. The intrusion exhibits a vertical continuum of compositions created by in situ fractional crystallisation of a single injection of magma in a closed igneous system and, as such, constitutes a natural laboratory amenable to determining the causes of Fe isotope fractionation in magmatic rocks. Early fractionation of pyroxenes and plagioclase, under conditions closed to oxygen exchange, gives rise to an iron enrichment trend and an increase in $ f_{{{\text{O}}_{2} }} $ of the melt relative to the Fayalite–Magnetite–Quartz (FMQ) buffer. Enrichment in Fe³⁺/ΣFe_melt is mirrored by δ⁵⁷Fe, where ^VIFe²⁺-bearing pyroxenes partition ⁵⁷Fe-depleted iron, defining an equilibrium pyroxene-melt fractionation factor of $ \Updelta^{57} {\text{Fe}}_{{{\text{px}} - {\text{melt}}}} \le - 0.25\,\permille \times 10^{6} /T^{2} $ . Upon magnetite saturation, the $ f_{{{\text{O}}_{2} }} $ and δ⁵⁷Fe of the melt fall, commensurate with the sequestration of the oxidised, ⁵⁷Fe-enriched iron into magnetite, quantified as $ \Updelta^{57} {\text{Fe}}_{{{\text{mtn}} - {\text{melt}}}} = + 0.20\,\permille \times 10^{6} /T^{2} $ . Pyroxene–magnetite pairs reveal an equilibrium fractionation factor of $ \Updelta^{57} {\text{Fe}}_{{{\text{mtn}} - {\text{px}}}} \approx + 0.30\,\permille $ at 900–1,000?°C. Iron isotopes in differentiated magmas suggest that they may act as an indicator of their oxidation state and tectonic setting.     

The R{\overline{3}} c \to R{\overline{3}} m transition in nitratine, NaNO3, and implications for calcite, CaCO3

The temperature dependences of the crystal structure and superstructure intensities in sodium nitrate, mineral name nitratine, NaNO₃, were studied using Rietveld structure refinements based on synchrotron powder X-ray diffraction. Nitratine transforms from $R{\overline{3}} c\;\hbox{to}\;R{\overline{3}} m$ at T _c = 552(1) K. A NO₃ group occupies, statistically, two positions with equal frequency in the disordered $R{\overline{3}} m$ phase, but with unequal frequency in the partially ordered $R{\overline{3}} c$ phase. One position for the NO₃ group is rotated by 60° or 180° with respect to the other. The occupancy of the two orientations in the $R{\overline{3}} c$ phase is obtained from the occupancy factor, x, for the O1 site and gives rise to the order parameter, S = 2x ? 1, where S is 0 at T _c and 1 at 0 K. The NO₃ groups rotate in a rapid process from about 541 to T _c, where the a axis contracts. Using a modified Bragg–Williams model, a good fit was obtained for the normalized intensities (that is, normalized, NI^1/2) for the (113) and (211) reflections in $R{\overline{3}} c\hbox {\,NaNO}_{3},$ and indicates a second-order transition. Using the same model, a reasonable fit was obtained for the order parameter, S, and also supports a second-order transition.     

Vigrishinite, Zn2Ti4 − x Si4O14(OH,H2O,□)8, a new mineral from the Lovozero alkaline complex, Kola Peninsula, Russia

A new mineral vigrishinite, epistolite-group member and first layer titanosilicate with species-defining Zn, was found at Mt. Malyi Punkaruaiv, in the Lovozero alkaline complex, Kola Peninsula, Russia. It occurs in a hydrothermally altered peralkaline pegmatite and is associated with microcline, ussingite, aegirine, analcime, gmelinite-Na, and chabazite-Ca. Vigrishinite forms rectangular or irregularly shaped lamellae up to 0.05 × 2 × 3 cm flattened on [001]. They are typically slightly split and show blocky character. The mineral is translucent to transparent and pale pink, yellowish-pinkish or colorless. The luster is vitreous. The Mohs’ hardness is 2.5–3. Vigrishinite is brittle. Cleavage is {001} perfect. D _meas = 3.03(2), D _calc = 2.97 g/cm³. The mineral is optically biaxial (?), α = 1.755(5), β = 1.82(1), γ = 1.835(8), 2V _meas = 45(10)°, 2V _calc = 50°. IR spectrum is given. The chemical composition (wt %; average of 9 point analyses, H₂O is determined by modified Penfield method) is as follows: 0.98 Na₂O, 0.30 K₂O, 0.56 CaO, 0.05 SrO, 0.44 BaO, 0.36 MgO, 2.09 MnO, 14.39 ZnO, 2.00 Fe₂O₃, 0.36 Al₂O₃, 32.29 SiO₂, 29.14 TiO₂, 2.08 ZrO₂, 7.34 Nb₂O₅, 0.46 F, 9.1 H₂O, ?0.19 O=F₂, total is 101.75. The empirical formula calculated on the basis of Si + Al = 4 is: H_7.42(Zn_1.30Na_0.23Mn_0.22Ca_0.07Mg_0.07K_0.05Ba_0.02)_Σ1.96(Ti_2.68Nb_0.41Fe _0.18 ³⁺ Zr_0.12)_Σ3.39(Si_3.95Al_0.05)_{Σ4 20.31}F_0.18. The simplified formula is: Zn₂Ti_4?x Si₄O₁₄(OH,H₂O,□)₈ (x < 1). Vigrishinite is triclinic, space group P $\bar 1$ , a = 8.743(9), b = 8.698(9), c = 11.581(11)Å, α = 91.54(8)°, β = 98.29(8)°, γ = 105.65(8)°, V = 837.2(1.5) ų, Z = 2. The strongest reflections in the X-ray powder pattern (d, Å, ?I[hkl]) are: 11.7-67[001], 8.27-50[100], 6.94-43[0 $\bar 1$ 1, $\bar 1$ 10], 5.73–54[1 $\bar 1$ 1, 002], 4.17-65[020, $\bar 1$ $\bar 1$ 2, 200], and 2.861-100[3 $\bar 1$ 0, 2 $\bar 2$ 2, 004, 1 $\bar 3$ 1]. The crystal structure model was obtained on a single crystal, R = 0.171. Vigrishinite and murmanite are close in the structure of the TiSiO motif, but strongly differ from each other in part of large cations and H-bearing groups. Vigrishinite is named in honor of Viktor G. Grishin (b. 1953), a Russian amateur mineralogist and mineral collector, to pay tribute to his contribution to the mineralogy of the Lovozero Complex. The type specimen is deposited in the Fersman Mineralogical Museum of Russian Academy of Sciences, Moscow.     

Alteration of Residual Circulation Due to Large-Scale Infrastructure in a Coastal Plain Estuary

Large-scale human-built infrastructure is shown to alter the salinity and subtidal residual flow in a realistic numerical simulation of hydrodynamic circulation in a coastal plain estuary (Tampa Bay). Two model scenarios are considered. The first uses a modern bathymetry and boundary conditions from the years 2001–2003. The second is identical to the first except that the bathymetry is based on depth soundings from the pre-construction year 1879. Differences between the models' output can only result from changes in bay morphology, in particular built infrastructure such as bridges, causeways, and dredging of the shipping channel. Thirty-day means of model output are calculated to remove the dominant tidal signals and allow examination of the subtidal dynamics. Infrastructure is found to steepen the mean axial salinity gradient $ \partial \overline{s}/ dx $ by ~40% when there is low freshwater input but flatten $ \partial \overline{s}/ dx $ by ~25% under more typical conditions during moderate freshwater inflow to the estuary. Deepening of the shipping channel also increases the magnitude of the residual Eulerian circulation, allowing for larger up-estuary salt transport. Local bathymetry and morphology are important. Some regions within the estuary show little change in residual circulation due to infrastructure. In others, the residual circulation can vary by a factor of 4 or more. Major features of the circulation and changes due to infrastructure can be partially accounted for with linear theory.     

Low dispersive modeling of Rayleigh waves on partly staggered grids

In elastic media, finite-difference (FD) implementations of free-surface (FS) boundary conditions on partly staggered grid (PSG) use the highly dispersive vacuum formulation (VPSG). The FS boundary is embedded into a “vacuum” grid layer (null Lame’s constants and negligible density values) where the discretized equations of motion allow computing surface displacements. We place a new set of compound (stress-displacement) nodes along a planar FS and use unilateral mimetic FD discretization of the zero-traction conditions for displacement computation (MPSG). At interior nodes, MPSG reduces to standard VPSG methods and applies fourth-order centered FD along cell diagonals for staggered differentiation combined with nodal second-order FD in time. We perform a dispersion analysis of these methods on a Lamb’s problem and estimate dispersion curves from the phase difference of windowed numerical Rayleigh pulses at two FS receivers. For a given grid sampling criterion (e.g., six or ten nodes per reference S wavelength λ ^S), MPSG dispersion errors are only a quarter of the VPSG method. We also quantify root-mean-square (RMS) misfits of numerical time series relative to analytical waveforms. MPSG RMS misfits barely exceed 10 % when nine nodes sample the minimum S wavelength $\lambda _{\text {MIN}}^{\mathrm {S}}$ in transit (along distances $\sim $ 145 $\lambda _{\text {MIN}}^{\mathrm {S}}$ ). In same tests, VPSG RMS misfits exceed 70 %. We additionally compare MPSG to a consistently fourth-order mimetic method designed on a standard staggered grid. The latter equates the former’s dispersion errors on grids twice denser and shows higher RMS precision only on grids with six or less nodes per $\lambda _{\text {MIN}}^{\mathrm {S}}$ .     

Groundwater use by plants in a semi-arid coal-mining area at the Mu Us Desert frontier

The hydrogen isotope (deuterium- $ \delta D $ ) composition at natural abundance levels of xylem water, soil water, groundwater, river water, and rainwater was used to evaluate whether adult plant species use groundwater and to detect seasonal shifts (dry/wet season) in water sources for plants growing in a semi-arid coal-mining area (located at the frontier of the Mu Us Desert). A direct inference approach and the IsoSource mixing model were used to estimate the contributions of different sources to the plant xylem water. The results showed that (1) the $ \delta D $ values of rainfall fluctuated considerably, while those of groundwater were generally constant during the experimental period; (2) the $ \delta D $ patterns in plant xylem water suggest that groundwater was a significant source of water for transpiration in the dry season, while all five selected species reduced dependence on groundwater sources in the wet season; and (3) soil water from the deep layer (50–100 cm) was used largely by adult species possibly because of interspecific competition. These results indicated that coal mining would significantly affect plant growth by reducing the water supply if it leads to a water table decrease. Therefore, it is necessary to protect groundwater resources during the coal mining operations in the region.